CN103509153A - Polymer single-ion electrolyte and preparation method thereof - Google Patents
Polymer single-ion electrolyte and preparation method thereof Download PDFInfo
- Publication number
- CN103509153A CN103509153A CN201210223926.8A CN201210223926A CN103509153A CN 103509153 A CN103509153 A CN 103509153A CN 201210223926 A CN201210223926 A CN 201210223926A CN 103509153 A CN103509153 A CN 103509153A
- Authority
- CN
- China
- Prior art keywords
- sulphonyl
- lithium
- reaction
- ion
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 *S([N-]S(c1ccc(C=C)cc1)(=O)=O)(=O)=O Chemical compound *S([N-]S(c1ccc(C=C)cc1)(=O)=O)(=O)=O 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses random copolymerization single-ion polymer electrolyte or block copolymerization single-ion polymer electrolyte which is obtained through copolymerization between a (p-vinyl phenylsulfonyl) (perfluoroalkyl sulfonyl) lithium imide monomer and a methoxyl polyethylene glycol acrylate monomer, and a preparation method of the electrolyte. The polymer single-ion electrolyte prepared by the method disclosed by the invention has the advantages of high room-temperature conductivity, high lithium ion transference number, low glass state temperature and degree of crystallinity, good mechanical strength and film-forming properties, wide electrochemical window, good thermal stability and the like, and has potential application values in the aspects of lithium (ion) batteries, carbon-based super-capacitors, solar batteries and the like.
Description
Technical field
The invention belongs to organic polymer functional materials and technical field of electrochemistry, relate to polymkeric substance list ionic electrolytes and preparation method thereof.
Background technology
Lithium ion battery has energy density and output voltage is high, memory-less effect, advantages of environment protection, has been widely used in the fields such as electronics, space flight, electric vehicle.At present, the electrolytic solution of commercialization secondary lithium battery mainly by conducting salt (as lithium hexafluoro phosphate, LiPF
6), organic carbonate ester solvent (as methylcarbonate (DMC), diethyl carbonate (DEC) vinyl carbonate (EC) etc.) and necessary functional additive be (as SEI membrane-forming agent, anti-overshoot additive, fire retardant, LiPF
6stablizer etc.) form (Chemical Review, 2004,104,4303; Journal ofPower Sources, 2006,162,1379).But in this non-aqueous solution electrolysis liquid system, the inflammable and easy volatile of organic carbonate, is the main potential safety hazard (as burning, blast, leaks etc.) of current lithium (ion) battery.Conducting salt LiPF
6there is thermolability and be easy to the intrinsic physicochemical property defects such as hydrolysis, be cause lithium ion battery in high-temperature zone (as>55 ° of C) one of the quick deteriorated major reason of performance.
Compare with liquid electrolyte, polymer dielectric have can suppress dendrite growth, reduce ionogen and interelectrode reactive behavior, safe and reliable, be easy to the advantages such as processing, be considered to overcome current liquid electrolyte defect, improve the novel electrolytes material of lithium (ion) battery performance.Common polymer dielectric is mainly divided into two classes.
The composite polymer electrolyte that one class is comprised of macromolecular compound and conducting salt (inorganic or organic lithium salt).Macromolecular compound mainly contains Pluronic F-127 (PEO), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polyvinylidene difluoride (PVDF) (PVdF) etc., and conducting salt is mainly LiPF
6, (LiClO in perchloric acid
4), LiBF4 (LiBF
4), trifluoromethyl sulfonic acid lithium (LiOSO
2cF
3), two (trifluoromethyl) imine lithium (LiN (SO
2cF
3)
2, LiTFSI) etc.In order to reduce the degree of crystallinity of polymkeric substance, improve electrolytical specific conductivity, some inorganic nano-particles or organic softening agent sometimes also can adulterate.Therefore, according to this class ionogen of form, can divide into again solid polymer electrolyte (SPE) and gel polymer electrolyte (GPE).In prior art, existing a large amount of research work around this base polymer compound electrolyte material launch (as CN102324559, CN102318125, CN102306832, CN102117932, CN102064340, CN102005611, CN101901938, CN101735589, CN101466750, CN1320979, CN101130587, CN102324561 etc.).But in such ionogen, lithium salts is comprised of lithium ion and inorganic or organic anion, can there is dissociation in all kinds of lithium salts, form lithium ion, negatively charged ion and ion pair after mixing polymeric matrix.In the charge and discharge process of battery, yin, yang ion will be distinguished anode and cathodic migration, and because the electric density of lithium ion is large, rate of migration is slow; Negatively charged ion moves comparatively fast, thereby causes occurring concentration gradient producing the polarizing potential contrary with extra electric field in ionogen, and its result can cause the ionic conductivity of material to decay in time and rapidly, significantly reduces the energy efficiency of battery.The lithium ion transference number t of most of SPE
+between 0.2～0.5, what have is even less than 0.1, and this has limited the application of SPE greatly.
Polymkeric substance list ionic electrolytes is another kind of polymer dielectric.Polymkeric substance list ionic electrolytes refers to negatively charged ion is fixed on main polymer chain, only has positively charged ion to move.For polymkeric substance single ion conductor, lithium ion transference number t+ is essentially 1.Compare with aforesaid composite solid polymer dielectric, because its negatively charged ion is fixed on main polymer chain, in charge and discharge process, can not produce because zwitterion travelling speed is different concentration polarization.
At present, in domestic and international prior art, the work of Study Polymer Melts list ionic electrolytes is a lot.Park etc. will gather vinyl benzenesulfonic acid lithium and polyoxyethylene (PEO) blend, obtain Polymer list ionic electrolytes (Electrochim.Acta, 2004,50,375).But because the degree of crystallinity of PEO is very high less with liberation degree Phenylsulfonic acid lithium, the room-temperature conductivity of this polymkeric substance list ionic electrolytes only has 3 * 10-5mS/cm.Sun etc., by the method for grafting, have synthesized a series of cancellated polymkeric substance list ionic electrolytes (Macromolecules, 2004,37,2219) that have.This type of cancellated polymkeric substance list ionic electrolytes synthesis step is loaded down with trivial details, synthesis condition is harsh, and its specific conductivity is also very low.When in crosslinked side chain, the number of unit of oxygen ethene is 5, the room-temperature conductivity of this type of network polymer single ion conductor is the highest, is only 3.5 * 10-4 mS/cm.Sun etc. also, respectively by free-radical polymerized and method grafting, have synthesized polymkeric substance list ionic electrolytes PAE8-co-E3SO3Li and the PAE8-g-EnSO3Li(Electrochim.Acta of two kinds of pectinations, 2005,50,1139).The room-temperature conductivity of this all solid state single ion conductor is not high equally, and when oxygen ethylene unit/lithium ion (EO/Li+) mol ratio is 40, now the room-temperature conductivity of single ionic electrolytes PAE8-co-E3SO3Li is the highest, is 2.0 * 10-4 mS/cm.Sadoway etc. have synthesized random copolymerization type polymkeric substance list ionic electrolytes P (OEM-r-LiMA)-g-PDMS(J.Electrochem.Soc.2005, and 152, A2281).Object based on improving room-temperature conductivity; author has done following improvement and optimization to this polymeric system: (1) is by reacting with Lewis acid BF3; the negatively charged ion of system is converted into the borate anion that electric density is disperseed more by carboxylate radical, so specific conductivity two orders of magnitude have been promoted; (2) author is again to the graft copolymer (POEM-g-PDMS) of polydimethylsiloxane (PDMS) with methoxy polyethylene glycol methacrylate-styrene polymer (POEM) that adulterate in above-mentioned system, in order to lithium concentration in telomerized polymer, reach best oxygen ethylene unit/lithium ion (EO/Li+) mol ratio.But improve and to optimize later single ion conductor room-temperature conductivity still lower, only up to 7 * 10-3 mS/cm.Allcock etc. synthesized take polyphosphonitrile as parent, take the comb-shaped polymer list ionic electrolytes that methoxyl group multicondensed ethylene glycol (MPEG) and (benzene sulfonyl) (trimethyl fluoride sulfonyl) imine lithium be side chain, along with increasing of methoxyl group multicondensed ethylene glycol side chain number, the specific conductivity of the type list ionic electrolytes is increasing gradually, its room-temperature conductivity is up to 2.45 * 10-3 mS/cm(Solid State Ionics, 2006,177,741).Zhang Peng etc. have reported a kind of single-ion polymer ionogen based on polyvinyl alcohol, by polyvinyl alcohol and borax generation gelation reaction, make the hydroxyl generation polycondensation on tetrafluoroborate (BF4-) negatively charged ion and polyvinyl alcohol, thereby prepare negatively charged ion and be fixed on the conductive polymer membrane on polyvinyl alcohol skeleton, specific conductivity reaches 0.4mS/cm(CN101891848).
Hallac etc. receive the methoxyl group multicondensed ethylene glycol (MPEG) of different molecular weight on the sulfimide lithium monomer of two (perfluoroalkyl) replacement by addition reaction, obtain the room-temperature ion melting salt (Electrochim.Acta of a series of different chain length, 2008,53,5985).Because perfluoroalkyl has the electronic effect of haling, the negative charge density of this kind of imine negatively charged ion is disperseed, cause its lattice energy very low, in addition the viscosity of this serial ion melting salt is low than the polymer dielectric of high molecular, so its specific conductivity is higher than traditional single ion conductor; When M (MPEG)=550, in the time of 120 ℃, specific conductivity is 1mS/cm; In the time of 60 ℃, specific conductivity approaches 0.1mS/cm.Although the specific conductivity of this class ion melting salt is very high, under its room temperature, be thick liquid, physical strength and film-forming properties are very poor, and this class ion melting salt can not be referred to as solid electrolyte strictly.Herath etc. have synthesized two kinds of serial ion melting salts containing (benzene sulfonyl) (trimethyl fluoride sulfonyl) imine lithium group, are respectively single anion type and dual anion type (Electrochim.Acta, 2009,54,5877).When oxygen ethylene unit/lithium ion (EO/Li+) is 11.8, the room-temperature conductivity of single anion type ion melting salt is the highest, is 2.7 * 10-3mS/cm.But, under its room temperature, being similarly thick liquid, this class ion melting salt can not be referred to as solid electrolyte strictly.
In sum,, there is the problems such as synthesis step loaded down with trivial details (netted single ion conductor), room-temperature conductivity lower (generally only having 10-4-10-5mS/cm), physical strength and film forming properties poor (ion melting salt) more in polymkeric substance list ionic electrolytes of the prior art.
Summary of the invention
The object of the present invention is to provide a kind of random copolymerization single-ion polymer ionogen being obtained by (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer and the copolymerization of methoxyl group multicondensed ethylene glycol acrylate monomer, or block copolymerization single-ion polymer list ionic electrolytes, its general structure is as shown in formula I:
In formula I, R is H or CH
3, n is the integer of 2-20, R
f=C
mh
2m+1, m=0-8;
Formula I polymkeric substance list ionic electrolytes number-average molecular weight be 2000-150000g/mol, preferred number average molecular weight is 20000-50000g/mol;
When formula I is block polymer Poly (LiSR
ffSI-b-MPEGA)) time: x is the integer of 5-500; Y is the integer of 2-500, and the number-average molecular weight of A block is 500-25000g/mol, and the number-average molecular weight of B block is 1000-120000g/mol.
The polymer dielectric of formula I can be that (be called for short MPEGA, (formula II) and (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium (is called for short Li[SR to methoxyl group multicondensed ethylene glycol acrylate
ffSI], formula III) random copolymers of two kinds of monomers is (hereinafter to be referred as Poly (LiSR
ffSI-co-MPEGA)), or the block polymer A-B of these two kinds of monomers (hereinafter to be referred as Poly (LiSR
ffSI-b-MPEGA)).
In formula II, R is H or CH
3; N is the integer of 2-20.
In formula III, R
f=C
mh
2m+1, m is the integer of 0-8.
Another object of the present invention is to provide a kind of random copolymerization single-ion polymer ionogen being obtained by (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer and the copolymerization of methoxyl group multicondensed ethylene glycol acrylate monomer, or the preparation method of block copolymerization single-ion polymer list ionic electrolytes (formula I).
The preparation method of random copolymers is to make (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer and methoxyl group multicondensed ethylene glycol acrylate monomer, under radical initiator causes, copolyreaction occur and form Random copolymer compound.The described concrete grammar that makes (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer and methoxyl group multicondensed ethylene glycol acrylate monomer that copolyreaction formation Random copolymer compound occurs under radical initiator causes is: by (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium (formula III) monomer and methoxyl group multicondensed ethylene glycol acrylate (formula II) monomer, according to stoichiometry mol ratio 1:1 ~ 1:20, preferably 1:8 joins in reaction vessel, then according to volume ratio 1:1 ~ 1:5, add solvent N, the initiator azo isobutyronitrile of dinethylformamide (DMF) and monomer molar total amount 0.5 ~ 5%, logical argon gas deoxygenation 2h, at 50 ~ 100 ℃, preferably 60 ℃, reaction 8 ~ 20h, preferred 15h, after completion of the reaction, be cooled to room temperature, under agitation, reaction solution is slowly splashed in excessive ether, make its Precipitation stick colloidal solid, the ether on upper strata is slowly poured out, so dissolve, precipitation three times repeatedly, obtain gelatinous polymer solid, by viscose shaped polymer vacuum-drying 8h at 80 ℃, obtain the random copolymers Poly (LiSR of formula I
ffSI-co-MPEGA),
The preparation method of block polymer is: make (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer and methoxyl group multicondensed ethylene glycol acrylate monomer generation block polymerization reaction form block polymer, described block polymerization reaction can be free radical block copolymerization reaction, negative ion block copolymerization reaction or positive ion block copolymerization reaction.Present patent application embodiment 8-10 has provided the specific implementation method of free radical block copolymerization reaction, is called reversible addition fracture radical polymerization (RAFT) in embodiment.The concrete grammar that makes (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer and methoxyl group multicondensed ethylene glycol acrylate monomer generation free radical block copolymerization reaction form block polymer comprises the following steps:
Step (one): will there is the methoxyl group multicondensed ethylene glycol acrylate monomer of formula II structure, dithiobenzoic acid isopropyl cyanide ester, azo isobutyronitrile is mixed to get mixture according to mass ratio 1:0.002:0.001 ~ 1:0.25:0.01, by this mixture and toluene solvant by volume the ratio of 1:1 ~ 1:3 add in reaction vessel, logical argon gas deoxygenation 2 hours, at 60 ~ 90 ℃, preferably 75 ℃, reaction 10 ~ 20h, preferably 12 hours, be chilled to room temperature, with ether sedimentation, after vacuum-drying, obtain the reversible addition fracture of macromole radical polymerization (RAFT) reagent of methoxyl group multicondensed ethylene glycol polyacrylic ester,
Step (two): will there is (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer of formula III structure, the reversible addition fracture of macromole radical polymerization (RAFT) reagent of methoxyl group multicondensed ethylene glycol polyacrylic ester prepared by step (), azo isobutyronitrile is mixed to get mixture according to mass ratio 1:1:0.001 ~ 1:10:0.03, by this mixture and DMF solvent by volume for the ratio of 1:0.5 ~ 1:2 adds in reaction vessel, logical argon gas deoxygenation 2 hours, at 60 ~ 90 ℃, preferably 70 ℃, react 15 ~ 28 hours, preferably 20 hours, be chilled to room temperature, with ether sedimentation, after vacuum-drying, obtain having the block polymer of formula I structure, obtain the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock Poly (LiSR of formula I
ffSI-b-MPEGA).
Random copolymers provided by the invention or block polymer can form polymkeric substance list ionic electrolytes, can apply as ionogen, as can be used as lithium ion battery electrolyte or lithium cell electrolyte.Specifically random copolymers provided by the invention or block polymer can be prepared into polymer electrolyte film, this polymer electrolyte film is the transparent film preparing by the following method: random copolymers provided by the invention or block polymer are dissolved in the methyl alcohol of 2 ~ 5 volumes, under stirring, dissolve completely latter standing 10 to 20 hours, preferably within 12 hours, obtain thick solution, this thick solution is poured on smooth polytetrafluoroethylene (PTFE) flat board, room temperature is placed 15 to 30 hours, preferably 24 hours, its solvent methanol is volatilized naturally, at 60 ~ 80 ℃, vacuum-drying is 24 to 50 hours, preferably 48 hours, obtain smooth surface, thickness is the transparent film of 50-300 μ m.
Another object of the present invention is to provide a kind of lithium ion battery or lithium cell that uses above-mentioned polymkeric substance list ionic electrolytes.
The polymkeric substance list ionic electrolytes tool of preparing in the present invention has the following advantages: (1) is due to the strong sucting electronic effect of perfluoroalkyl and the conjugative effect of phenyl ring, the two synergy has reduced the negative charge density on N atom, thereby impel sulfimide lithium liberation degree to increase, current carrier number increases, and is conducive to improve room-temperature conductivity.(2) single ion conductor of preparing by the method for copolymerization is amorphous state, has reduced the degree of crystallinity of polymkeric substance, is conducive to improve the specific conductivity of polymkeric substance single ion conductor.(3) polyoxyethylene-(CH
2cH
2o)
ngeneral and the EO/Li of the specific conductivity of-type single ion conductor
+mol ratio is relevant.Can be by changing two kinds of monomeric charge ratios or methoxyl group multicondensed ethylene glycol (CH in the present invention
3o (CH
2cH
2o)
n-) chain length, prepare any different EO/Li
+the single ion conductor of mol ratio; Find out different EO/Li
+rule between mol ratio and specific conductivity, reaches the EO/Li that selects to have high conductivity
+mol ratio object.
Polymkeric substance list ionic electrolytes prepared by the present invention has that room-temperature conductivity is high, lithium ion transference number is high, second-order transition temperature and degree of crystallinity is low, physical strength and film forming properties is good, electrochemical window is wide and the advantage such as Heat stability is good, at aspects such as lithium (ion) battery, carbon back ultracapacitor and solar cells, has potential using value.
Accompanying drawing explanation
Fig. 1: the film photo of ionogen 2 (Poly (LiSTFSI-co-MPEGA, n=8));
Fig. 2: different EO/Li
+than the specific conductivity variation with temperature figure of Poly (LiSTFSI-co-MPEGA);
Embodiment
Enumerate the preparation of part of compounds involved in the present invention below, and the performance test results, so that the present invention is further detailed explanation, but be not restricted to cited compound.
Embodiment 1-10 is the preparation of polymkeric substance list ionic electrolytes
Embodiment 1:(is to Ethenylbenzene sulphonyl) preparation of (fluorine sulphonyl) imine lithium (LiSFSI) and methoxyl group triethylene Glycol acrylate (MPEGA, n=3) multipolymer (ionogen 1)
To the methoxyl group triethylene Glycol acrylate (MPEGA, n=3), 0.0042g (0.025mmol) Diisopropyl azodicarboxylate (AIBN) and the dry DMF of 2.5mL that add 1.32g (5.0mmol) (to Ethenylbenzene sulphonyl) (fluorine sulphonyl) imine lithium (LiSFSI) monomer, 1.09g (5.0mmol) in the reaction flask of 25mL.Logical argon gas deoxygenation 2h reacts 8h at 50 ℃.After completion of the reaction, be cooled to room temperature, under agitation, reaction solution slowly splashed in excessive ether, the ether on the glutinous colloidal solid ，Jiang of its Precipitation upper strata is slowly poured out, so dissolve, precipitate three times repeatedly, obtain gelatinous polymer solid; By viscose shaped polymer vacuum-drying 8h at 80 ℃, obtain random copolymers (ionogen 1) 1.6g.By nuclear-magnetism, characterize, calculate oxygen ethylene unit (EO) actual in product and lithium ion (Li
+) mol ratio (EO/Li
+) be 3.9.
By the above-mentioned 1.6g random copolymers Poly (LiSFSI-co-MPEGA) preparing, be dissolved in the CH of 4.0mL
3in OH, hold over night after dissolving completely under stirring.By the method for toppling over, it is laid on smooth polytetrafluoroethylene (PTFE) flat board thick solution, room temperature is placed 24h, makes its solvent C H
3oH volatilizees naturally, and vacuum-drying 48h at 60 ℃ obtains smooth surface, thickness is 50 μ m and the transparent film (ionogen 1) with certain physical strength.
Embodiment 2:(is to Ethenylbenzene sulphonyl) preparation of (trimethyl fluoride sulfonyl) imine lithium (LiSTFSI) and methoxyl group eight condensed ethandiol acrylate (MPEGA, n=8) multipolymers (ionogen 2)
To methoxyl group eight condensed ethandiols (400) acrylate (MPEGA, n=8), 0.013g (0.08mmol) Diisopropyl azodicarboxylate (AIBN) and the dry DMF of 5mL that add 1.32g (4.1mmol) (to Ethenylbenzene sulphonyl) (trimethyl fluoride sulfonyl) imine lithium (LiSTFSI) monomer, 1.80g (3.7mmol) in the reaction flask of 25mL.Logical argon gas deoxygenation 2h reacts 15h at 60 ℃.After completion of the reaction, be cooled to room temperature, under agitation, reaction solution slowly splashed in excessive ether, the ether on the glutinous colloidal solid ，Jiang of its Precipitation upper strata is slowly poured out, so dissolve, precipitate three times repeatedly, obtain gelatinous polymer solid; By viscose shaped polymer vacuum-drying 8h at 80 ℃, obtain random copolymers (ionogen 2) 42g.
By the above-mentioned 42g random copolymers Poly (LiSTFSI-co-MPEGA) preparing, be dissolved in the CH of 10mL
3in OH, hold over night after dissolving completely under stirring.By the method for toppling over, it is laid on smooth polytetrafluoroethylene (PTFE) flat board thick solution, room temperature is placed 24h, makes its solvent C H
3oH volatilizees naturally, and vacuum-drying 48h at 60 ℃ obtains smooth surface, thickness is 85 μ m and the transparent film (ionogen 2) with certain physical strength.
The structure of the multipolymer that the present embodiment is prepared characterizes by nucleus magnetic resonance, and Fig. 3 is shown in by collection of illustrative plates, its
1hNMR data are as follows:
1H NMR(399.76MHz;DMSO-d
6;TMS):δ=1.56(broad,5H),δ=3.22,3.41,3.49and 4.08(broad,28H),δ=7.02(broad,2H),δ=7.56(broad,2H).
19F NMR(376.05MHz;DMSO-d
6;CCl
3F):-77.8(s).
According to multipolymer
1in H NMR, H atom peak area and the contained group methoxy poly (ethylene glycol) of another monomer (CH on phenyl ring
3(OCH
2cH
2)
8-) the integration ratio of whole H atom peak areas, calculate oxygen ethylene unit (EO) actual in product and lithium ion (Li
+) mol ratio (EO/Li
+) be 6.71.
Embodiment 3:(is to Ethenylbenzene sulphonyl) preparation of (trimethyl fluoride sulfonyl) imine lithium (LiSTFSI) and methoxyl group five condensed ethandiol acrylate (MPEGA, n=5) multipolymers (ionogen 3)
To the methoxyl group five condensed ethandiol acrylate (MPEGA, n=5), 0.0078g (0.047mmol) Diisopropyl azodicarboxylate and the dry DMF of 15mL that add 1.42g (4.7mmol) (to Ethenylbenzene sulphonyl) (trimethyl fluoride sulfonyl) imine lithium (LiSTFSI) monomer 7.89g (23.5mmol) in the reaction flask of 25mL.Logical argon gas deoxygenation 2h reacts 20h at 70 ℃.After completion of the reaction, be cooled to room temperature, under agitation, reaction solution slowly splashed in excessive ether, the ether on the glutinous colloidal solid ，Jiang of its Precipitation upper strata is slowly poured out, so dissolve, precipitate three times repeatedly, obtain gelatinous polymer solid; By viscose shaped polymer vacuum-drying 8h at 80 ℃, obtain random copolymers (ionogen 3) 7.8g.By nuclear-magnetism, characterize, calculate oxygen ethylene unit (EO) actual in product and lithium ion (Li
+) mol ratio (EO/Li
+) be 12.4.
By the above-mentioned 1.52g random copolymers Poly (LiSTFSI-co-MPEGA) preparing, be dissolved in the CH of 5mL
3in OH, hold over night after dissolving completely under stirring.By the method for toppling over, it is laid on smooth polytetrafluoroethylene (PTFE) flat board thick solution, room temperature is placed 24h, makes its solvent C H
3oH volatilizees naturally, and vacuum-drying 48h at 60 ℃ obtains smooth surface, thickness is 90 μ m and the transparent film (ionogen 3) with certain physical strength.
Embodiment 4:(is to Ethenylbenzene sulphonyl) preparation of (trimethyl fluoride sulfonyl) imine lithium (LiSTFSI) and methoxy polyethylene glycol acrylate (MPEGA, n=20) multipolymer (ionogen 4)
To the methoxy polyethylene glycol acrylate (MPEGA, n=20), 0.046g (0.275mmol) Diisopropyl azodicarboxylate and the dry DMF of 25mL that add 1.68g (5.5mmol) (to Ethenylbenzene sulphonyl) (trimethyl fluoride sulfonyl) imine lithium (LiSTFSI) monomer 9.68g (11.0mmol) in the reaction flask of 50mL.Logical argon gas deoxygenation 2h reacts 18h at 80 ℃.After completion of the reaction, be cooled to room temperature, under agitation, reaction solution slowly splashed in excessive ether, the ether on the glutinous colloidal solid ，Jiang of its Precipitation upper strata is slowly poured out, so dissolve, precipitate three times repeatedly, obtain gelatinous polymer solid; By viscose shaped polymer vacuum-drying 8h at 80 ℃, obtain random copolymers (ionogen 4) 8.9g.By nuclear-magnetism, characterize, calculate oxygen ethylene unit (EO) actual in product and lithium ion (Li
+) mol ratio (EO/Li
+) be 19.6.
By the above-mentioned 2.32g random copolymers Poly (LiSTFSI-co-MPEGA) preparing, be dissolved in the CH of 15mL
3in OH, hold over night after dissolving completely under stirring.By the method for toppling over, it is laid on smooth polytetrafluoroethylene (PTFE) flat board thick solution, room temperature is placed 24h, makes its solvent C H
3oH volatilizees naturally, and vacuum-drying 48h at 70 ℃ obtains smooth surface, thickness is 100 μ m and the transparent film (ionogen 4) with certain physical strength.
Embodiment 5:(is to Ethenylbenzene sulphonyl) preparation of (pentafluoroethyl group sulphonyl) imine lithium (LiSPFSI) and methoxyl group eight condensed ethandiol acrylate (MPEGA, n=8) multipolymers (ionogen 5)
To methoxyl group eight condensed ethandiols (400) acrylate (MPEGA), 0.0065g (0.04mmol) Diisopropyl azodicarboxylate (AIBN) and the dry DMF of 15mL that add 1.50g (4.0mmol) (to Ethenylbenzene sulphonyl) (pentafluoroethyl group sulphonyl) imine lithium (LiSPFSI) monomer, 1.77g (4.1mmol) in the reaction flask of 25mL.Logical argon gas deoxygenation 2h reacts 18h at 70 ℃.After completion of the reaction, be cooled to room temperature, under agitation, reaction solution slowly splashed in excessive ether, the ether on the glutinous colloidal solid ，Jiang of its Precipitation upper strata is slowly poured out, so dissolve, precipitate three times repeatedly, obtain gelatinous polymer solid; By viscose shaped polymer vacuum-drying 8h at 80 ℃, obtain random copolymers (ionogen 5) 2.55g.By nuclear-magnetism, characterize, calculate oxygen ethylene unit (EO) actual in product and lithium ion (Li
+) mol ratio (EO/Li
+) be 7.27.
By the above-mentioned 2.55g random copolymers Poly (LiSPFSI-co-MPEGA) preparing, be dissolved in the CH of 6mL
3in OH, hold over night after dissolving completely under stirring.By the method for toppling over, it is laid on smooth polytetrafluoroethylene (PTFE) flat board thick solution, room temperature is placed 24h, makes its solvent C H
3oH volatilizees naturally, and vacuum-drying 48h at 65 ℃ obtains smooth surface, thickness is 60 μ m and the transparent film (ionogen 5) with certain physical strength.
Embodiment 6:(is to Ethenylbenzene sulphonyl) preparation of (perfluoro butyl sulphonyl) imine lithium (LiSNFSI) and methoxyl group eight condensed ethandiol acrylate (MPEGA, n=8) multipolymers (ionogen 6)
To methoxyl group eight condensed ethandiols (400) acrylate (MPEGA, n=8), 0.020g (0.12mmol) Diisopropyl azodicarboxylate and the dry DMF of 15mL that add 1.85g (3.9mmol) (to Ethenylbenzene sulphonyl) (perfluoro butyl sulphonyl) imine lithium (LiSNFSI) monomer, 1.81g (3.9mmol) in the reaction flask of 25mL.Logical argon gas deoxygenation 2h reacts 12h at 90 ℃.After completion of the reaction, be cooled to room temperature, under agitation, reaction solution slowly splashed in excessive ether, the ether on the glutinous colloidal solid ，Jiang of its Precipitation upper strata is slowly poured out, so dissolve, precipitate three times repeatedly, obtain gelatinous polymer solid; By viscose shaped polymer vacuum-drying 8h at 80 ℃, obtain random copolymers (ionogen 6) 3.01g.By nuclear-magnetism, characterize, calculate oxygen ethylene unit (EO) actual in product and lithium ion (Li
+) mol ratio (EO/Li
+) be 5.89.
By the above-mentioned 1.65g random copolymers Poly (LiSNFSI-co-MPEGA) preparing, be dissolved in the CH of 5mL
3in OH, hold over night after dissolving completely under stirring.By the method for toppling over, it is laid on smooth polytetrafluoroethylene (PTFE) flat board thick solution, room temperature is placed 24h, makes its solvent C H
3oH volatilizees naturally, and vacuum-drying 48h at 80 ℃ obtains smooth surface, thickness is 220 μ m and the transparent film (ionogen 6) with certain physical strength.
Embodiment 7:(is to Ethenylbenzene sulphonyl) preparation of (perfluoro capryl sulphonyl) imine lithium (LiSOFSI) and methoxyl group eight condensed ethandiol acrylate (MPEGA, n=8) multipolymers (ionogen 7)
To methoxyl group eight condensed ethandiols (400) acrylate (MPEGA, n=8), 0.016g (0.096mmol) Diisopropyl azodicarboxylate and the dry DMF of 15mL that add 2.79g (4.8mmol) (to Ethenylbenzene sulphonyl) (perfluoro butyl sulphonyl) imine lithium (LiSOFSI) monomer, 3.28g (7.5mmol) in the reaction flask of 25mL.Logical argon gas deoxygenation 2h reacts 20h at 100 ℃.After completion of the reaction, be cooled to room temperature, under agitation, reaction solution slowly splashed in excessive ether, the ether on the glutinous colloidal solid ，Jiang of its Precipitation upper strata is slowly poured out, so dissolve, precipitate three times repeatedly, obtain gelatinous polymer solid; By viscose shaped polymer vacuum-drying 8h at 80 ℃, obtain random copolymers ionogen 75.68g.By nuclear-magnetism, characterize, calculate oxygen ethylene unit (EO) actual in product and lithium ion (Li
+) mol ratio (EO/Li
+) be 9.32.
By the above-mentioned 1.85g random copolymers Poly (LiSNFSI-co-MPEGA) preparing, be dissolved in the CH of 15mL
3in OH, hold over night after dissolving completely under stirring.By the method for toppling over, it is laid on smooth polytetrafluoroethylene (PTFE) flat board thick solution, room temperature is placed 24h, makes its solvent C H
3oH volatilizees naturally, and vacuum-drying 48h at 70 ℃ obtains smooth surface, thickness is 300 μ m and the transparent film (ionogen 7) with certain physical strength.
Embodiment 8:(is to Ethenylbenzene sulphonyl) preparation of (trimethyl fluoride sulfonyl) imine lithium (LiSTFSI) and methoxyl group eight condensed ethandiol acrylate (MPEGA, n=8) segmented copolymers (ionogen 8)
To methoxyl group eight condensed ethandiols (400) acrylate (MPEGA, n=8), 0.0096g dithiobenzoic acid isopropyl cyanide ester, 0.0048g Diisopropyl azodicarboxylate (AIBN) and the dry toluene of 5mL that add 4.80g in the reaction flask of 25mL.Logical argon gas deoxygenation 2h reacts 10h at 60 ℃.Be chilled to room temperature, use after ether sedimentation, vacuum-drying, obtain the reversible addition fracture of macromole radical polymerization (RAFT) reagent (PMPEGA-RAFT) of 4.4g polymethoxy multicondensed ethylene glycol polyacrylic ester.
To the PMPEGA-RAFT reagent, 0.0045g and the 5mL DMF solvent that add 4.4g (to Ethenylbenzene sulphonyl) (trimethyl fluoride sulfonyl) imine lithium (LiSTFSI) monomer, the above-mentioned preparation of 4.4g in the reaction flask of 25mL.Logical argon gas deoxygenation 2h reacts 15h at 60 ℃.Be chilled to room temperature, use after ether sedimentation, vacuum-drying, obtain Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock Poly (LiSTFSI-b-MPEGA) (being ionogen 8) 5.6g.
By the above-mentioned 2.05g segmented copolymer Poly (LiSTFSI-b-MPEGA) preparing, be dissolved in the CH of 10mL
3in OH, hold over night after dissolving completely under stirring.By the method for toppling over, it is laid on smooth polytetrafluoroethylene (PTFE) flat board thick solution, room temperature is placed 24h, makes its solvent C H
3oH volatilizees naturally, and vacuum-drying 48h at 75 ℃ obtains smooth surface, thickness is 55 μ m and the transparent film (ionogen 8) with certain physical strength.
Embodiment 9:(is to Ethenylbenzene sulphonyl) preparation of (trimethyl fluoride sulfonyl) imine lithium (LiSTFSI) and methoxyl group eight condensed ethandiol acrylate (MPEGA, n=8) segmented copolymers (being ionogen 9)
To methoxyl group eight condensed ethandiols (400) acrylate (MPEGA, n=8), 0.24g dithiobenzoic acid isopropyl cyanide ester, 0.24g Diisopropyl azodicarboxylate and the dry toluene of 8mL that add 4.80g in the reaction flask of 25mL.Logical argon gas deoxygenation 2h reacts 12h at 75 ℃.Be chilled to room temperature, use after ether sedimentation, vacuum-drying, obtain the reversible addition fracture of macromole radical polymerization (RAFT) reagent (PMPEGA-RAFT) of 4.6g polymethoxy multicondensed ethylene glycol polyacrylic ester.
To the PMPEGA-RAFT reagent, 0.069g and the 12mL DMF solvent that add 4.6g (to Ethenylbenzene sulphonyl) (trimethyl fluoride sulfonyl) imine lithium (LiSTFSI) monomer, the above-mentioned preparation of 23g in the reaction flask of 50mL.Logical argon gas deoxygenation 2h reacts 20h at 70 ℃.Be chilled to room temperature, use after ether sedimentation, vacuum-drying, obtain Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock Poly (LiSTFSI-b-MPEGA) (the being ionogen 9) 18.5g of formula I.
By the above-mentioned 2.34g segmented copolymer Poly (LiSTFSI-b-MPEGA) preparing, be dissolved in the CH of 10mL
3in OH, hold over night after dissolving completely under stirring.By the method for toppling over, it is laid on smooth polytetrafluoroethylene (PTFE) flat board thick solution, room temperature is placed 24h, makes its solvent C H
3oH volatilizees naturally, and vacuum-drying 48h at 75 ℃ obtains smooth surface, thickness is 65 μ m and the transparent film (ionogen 9) with certain physical strength.
Embodiment 10:(is to Ethenylbenzene sulphonyl) preparation of (trimethyl fluoride sulfonyl) imine lithium (LiSTFSI) and methoxyl group eight condensed ethandiol acrylate (MPEGA, n=8) segmented copolymers (ionogen 10)
To methoxyl group eight condensed ethandiols (400) acrylate (MPEGA, n=8), 1.20g dithiobenzoic acid isopropyl cyanide ester, 0.48g Diisopropyl azodicarboxylate and the dry toluene of 15mL that add 4.80g in the reaction flask of 25mL.Logical argon gas deoxygenation 2h reacts 20h at 90 ℃.Be chilled to room temperature, use after ether sedimentation, vacuum-drying, obtain the reversible addition fracture of macromole radical polymerization (RAFT) reagent (PMPEGA-RAFT) of 5.4g polymethoxy multicondensed ethylene glycol polyacrylic ester.
To the PMPEGA-RAFT reagent, 0.138g and the 100mL DMF solvent that add 5.4g (to Ethenylbenzene sulphonyl) (trimethyl fluoride sulfonyl) imine lithium (LiSTFSI) monomer, the above-mentioned preparation of 54g in the reaction flask of 250mL.Logical argon gas deoxygenation 2h reacts 28h at 90 ℃.Be chilled to room temperature, use after ether sedimentation, vacuum-drying, obtain Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock Poly (LiSTFSI-b-MPEGA) (being ionogen 10) 34.8g.
By the above-mentioned 2.34g segmented copolymer Poly (LiSTFSI-b-MPEGA) preparing, be dissolved in the CH of 7mL
3in OH, hold over night after dissolving completely under stirring.By the method for toppling over, it is laid on smooth polytetrafluoroethylene (PTFE) flat board thick solution, room temperature is placed 24h, makes its solvent C H
3oH volatilizees naturally, and vacuum-drying 48h at 70 ℃ obtains smooth surface, thickness is 74 μ m and the transparent film (ionogen 10) with certain physical strength.
Embodiment 11: the performance characterization of the polymkeric substance list ionic electrolytes 1-10 of preparation
(1) mensuration of specific conductivity: use the electrochemical workstation Autolab PGSTAT302N of Switzerland Wan Tong company in the present invention, adopt electrochemical AC impedance spectrometry (Electrochemical Impedance Spectroscopy, EIS) to measure the ionic conductivity of polymer dielectric.
Polymer dielectric film is clipped between two stainless steel blocking electrodes of known surface area, in order to ensure electrode, contacts with ionogen well, before measuring, will measure system constant temperature 2h at 60 ℃.The temperature range of measuring is 25 to 90 ℃, and the frequency of measurement is 0.1-10
6hz.This body resistance that Nyquist figure by alternating-current impedance reads polymer dielectric, then according to formula σ=l/AR, calculates the conductivityσ of polymer dielectric film, the thickness that wherein l is film, and A is electrode area, this body resistance that R is polymer dielectric film.
(2) mensuration of transference number of ions: that adopt in the present invention is exactly (the P.G.Brrce et al such as Bruce, Polvmer, 1987,28,2324) and (the K.M.Abraham et al such as Abraham, Chem.Mater.1997,9,1978) improved alternating-current impedance-direct current polarization (AC-DC) coupling method mensuration lithium ion transference number.Single-ion polymer ionogen is assembled into symmetry model battery Li | SPEs | Li, probe temperature is 60 ℃, polarizing voltage is 100mV, ac impedance measurement range of frequency 0.01Hz to 1MHz.According to formula
(I wherein
s, I
obe respectively steady state current and primary state electric current (in direct current polarization figure, reading),
be respectively this body resistance of stable state and this body resistance of primary state (reading in impedance spectrum), Δ V is polarizing voltage (known, to be 100mV),
be respectively primary state interface resistance and stable state interface resistance (reading in impedance spectrum)), can calculate the lithium ion transference number of single ion conductor.
(3) electrochemical window is measured: in the present invention, use the logical Autolab PGSTAT302N type electrochemical workstation of Switzerland ten thousand, adopt linear sweep voltammetry (linear sweep voltammetry, LSV) measure oxidation, the reduction potential of polymer dielectric, then according to formula:
EW
s=E
anodic-E
cathodic
(wherein, EW
selectrochemical window for polymer dielectric; E
anodicoxidizing potential for polymer dielectric; E
cathodicreduction potential for polymer dielectric), can calculate the electrochemical window of polymer dielectric.
Adopt three-electrode system to measure redox potential; Wherein Pt is working electrode (electrode area: 7.85 * 10
-3cm
-2), metallic lithium is reference electrode and to electrode; Scanning speed is 5mVs
-1; Probe temperature is 25 ℃.
The results are shown in Table 1 in performance test.
The performance test results of table 1 single-ion polymer ionogen 1-10 (30 ° of C)
| Electrolysis | Specific conductivity | Electrification | Migration |
| 1 | 6.50x10 -3 | 5.88 | 0.93 |
| 2 | 3.91 | 6.01 | 0.96 |
| 3 | 2.64 | 5.99 | 0.95 |
| 4 | 3.69 | 6.00 | 0.94 |
| 5 | 7.92 | 6.12 | 0.95 |
| 6 | 3.85 | 6.24 | 0.96 |
| 7 | 3.36 | 6.45 | 0.95 |
| 8 | 1.78 | 6.03 | 0.97 |
| 9 | 3.57 | 6.00 | 0.96 |
| 10 | 2.88 | 5.97 | 0.96 |
Embodiment 12 application of single-ion polymer ionogen in lithium cell.
(1) positive pole: respectively with LiCoO
2, LiMn
2o
4, LiFePO
4, Li (CoNiMn)
1/3o
2deng the electrode slice that is active substance, it is positive pole.
(2) negative pole:, Li negative with lithium paper tinsel, synthetic graphite respectively
4ti
5o
12deng being negative pole.
(3) ionogen: take ionogen 2 or ionogen 9 single-ion polymers is ionogen.
(4) assembling of polymer battery: in argon gas glove box, above-mentioned positive pole, negative pole and ionogen are assembled into polymer battery.Upper at micro-processor controlled auto charge and discharge instrument (Land, CT2001A), carry out cycle performance of battery test.The test result of the present embodiment is referring to table 2.
The performance (30 ° C) of table 2 based on the electrolytical serondary lithium battery of single-ion polymer
Claims (11)
1. random copolymers or the block polymer with following formula I structure,
In formula I, R is H or CH
3, n is the integer of 2-20, R
f=C
mh
2m+1, m=0-8;
The number-average molecular weight of formula I polymkeric substance is 2000-150000g/mol, and preferred number average molecular weight is 20000-50000g/mol;
When formula I is block polymerization macromolecular compound: x is the integer of 5-500; Y is the integer of 2-500, and the number-average molecular weight of A block is 500-25000g/mol, and the number-average molecular weight of B block is 1000-120000g/mol.
2. the polymkeric substance list ionic electrolytes being formed by random copolymerization claimed in claim 1 or block polymerization macromolecular compound.
3. random copolymerization claimed in claim 1 or block polymerization macromolecular compound are applied as ionogen.
4. application according to claim 3, is characterized in that, described ionogen is lithium ion battery electrolyte or lithium cell electrolyte.
5. the preparation method of Random copolymer compound claimed in claim 1, it is characterized in that, make (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer and methoxyl group multicondensed ethylene glycol acrylate monomer, under radical initiator causes, copolyreaction occur and form Random copolymer compound.
6. the preparation method of block polymerization macromolecular compound claimed in claim 1, it is characterized in that, make (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer and methoxyl group multicondensed ethylene glycol acrylate monomer generation block polymerization reaction form block polymerization macromolecular compound.
7. the preparation method of block polymerization macromolecular compound claimed in claim 6, is characterized in that, described block polymerization reaction can be free radical block copolymerization reaction, negative ion block copolymerization reaction or positive ion block copolymerization reaction.
8. preparation method according to claim 5, it is characterized in that, the described concrete grammar that makes (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer and methoxyl group multicondensed ethylene glycol acrylate monomer that copolyreaction formation Random copolymer compound occurs under radical initiator causes is: will have formula II structure (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer and the methoxyl group multicondensed ethylene glycol acrylate monomer with formula III structure, according to stoichiometry mol ratio 1:1 ~ 1:20, preferably 1:8 joins in reaction vessel, then according to volume ratio 1:1 ~ 1:5, add solvent N, the initiator azo isobutyronitrile of dinethylformamide (DMF) and monomer molar total amount 0.5 ~ 5%, logical argon gas deoxygenation 2h, at 50 ~ 100 ℃, preferably 60 ℃, reaction 8 ~ 20h, preferred 15h, after completion of the reaction, be cooled to room temperature, under agitation, reaction solution is slowly splashed in excessive ether, make its Precipitation stick colloidal solid, the ether on upper strata is slowly poured out, so dissolve, precipitation three times repeatedly, obtain gelatinous polymer solid, by viscose shaped polymer vacuum-drying 8h at 80 ℃, obtain the random copolymers Poly (LiSR of formula I
ffSI-co-MPEGA),
9. preparation method according to claim 6, it is characterized in that, the concrete grammar that described making (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer and methoxyl group multicondensed ethylene glycol acrylate monomer generation block polymerization reaction form block polymerization macromolecular compound comprises the following steps:
Step (one): will there is the methoxyl group multicondensed ethylene glycol acrylate monomer of formula III structure, dithiobenzoic acid isopropyl cyanide ester, azo isobutyronitrile is mixed to get mixture according to mass ratio 1:0.002:0.001 ~ 1:0.25:0.01, by this mixture and toluene solvant by volume the ratio of 1:1 ~ 1:3 add in reaction vessel, logical argon gas deoxygenation 2 hours, at 60 ~ 90 ℃, preferably 75 ℃, reaction 10 ~ 20h, preferably 12 hours, be chilled to room temperature, with ether sedimentation, after vacuum-drying, obtain the reversible addition fracture of macromole radical polymerization (RAFT) reagent of methoxyl group multicondensed ethylene glycol polyacrylic ester,
Step (two): will there is (to Ethenylbenzene sulphonyl) (perfluoroalkyl sulphonyl) imine lithium monomer of formula II structure, the reversible addition fracture of macromole radical polymerization (RAFT) reagent of methoxyl group multicondensed ethylene glycol polyacrylic ester prepared by step (), azo isobutyronitrile is mixed to get mixture according to mass ratio 1:1:0.001 ~ 1:10:0.03, by this mixture and DMF solvent by volume for the ratio of 1:0.5 ~ 1:2 adds in reaction vessel, logical argon gas deoxygenation 2 hours, at 60 ~ 90 ℃, preferably 70 ℃, react 15 ~ 28 hours, preferably 20 hours, be chilled to room temperature, with ether sedimentation, after vacuum-drying, obtain having the block polymerization macromolecular compound of formula I structure.
10. a polymer electrolyte film, it is characterized in that it is the transparent film preparing by the following method: random copolymerization claimed in claim 1 or block polymerization macromolecular compound are dissolved in the methyl alcohol of 2 ~ 5 volumes, under stirring, dissolve completely latter standing 10 to 20 hours, preferably within 12 hours, obtain thick solution, this thick solution is poured on smooth polytetrafluoroethylene (PTFE) flat board, room temperature is placed 15 to 30 hours, preferably 24 hours, its solvent methanol is volatilized naturally, at 60 ~ 80 ℃, vacuum-drying is 24 to 50 hours, preferably 48 hours, obtain smooth surface, thickness is the transparent film of 50-300 μ m.
11. 1 kinds of lithium ion batteries or lithium cell, is characterized in that, its ionogen is polymkeric substance list ionic electrolytes claimed in claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210223926.8A CN103509153B (en) | 2012-06-15 | 2012-07-02 | A kind of polymer list ionic electrolytes and preparation method thereof |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101977912 | 2012-06-15 | ||
| CN201210197791 | 2012-06-15 | ||
| CN201210197791.2 | 2012-06-15 | ||
| CN201210223926.8A CN103509153B (en) | 2012-06-15 | 2012-07-02 | A kind of polymer list ionic electrolytes and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103509153A true CN103509153A (en) | 2014-01-15 |
| CN103509153B CN103509153B (en) | 2016-05-25 |
Family
ID=49892619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210223926.8A Active CN103509153B (en) | 2012-06-15 | 2012-07-02 | A kind of polymer list ionic electrolytes and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103509153B (en) |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410270A (en) * | 2016-11-04 | 2017-02-15 | 中山大学 | Single-lithium-ion-conducting solid polymer electrolyte adopting carbon dioxide based polycarbonate as main chain and preparation method of single-lithium-ion-conducting solid polymer electrolyte |
| CN106674391A (en) * | 2015-11-10 | 2017-05-17 | 华中科技大学 | Iamine-polyanion lithium salt and preparation method thereof as well as application of iamine-polyanion lithium salt as nonaqueous electrolyte |
| CN106711503A (en) * | 2016-12-19 | 2017-05-24 | 西南石油大学 | Single-ion gel polymer electrolyte and preparation method thereof |
| US9856341B2 (en) | 2014-12-26 | 2018-01-02 | Samsung Electronics Co., Ltd. | Polymer, and electrolyte and lithium secondary battery including the same |
| KR20180049949A (en) * | 2016-11-04 | 2018-05-14 | 주식회사 엘지화학 | Compound including aromatic ring, polymer including the same |
| CN108155414A (en) * | 2016-12-06 | 2018-06-12 | 中国科学院宁波材料技术与工程研究所 | Fluoropolymer lithium ion conductor, preparation method and the application of self-plasticization |
| WO2018161150A1 (en) * | 2017-03-09 | 2018-09-13 | Blue Solutions Canada Inc. | Block copolymer electrolyte for lithium batteries |
| CN108832178A (en) * | 2018-06-20 | 2018-11-16 | 哈尔滨工业大学 | single-ion polymer electrolyte and its preparation method and application |
| CN109096433A (en) * | 2017-06-20 | 2018-12-28 | 天津大学 | Single ion conductor polymer lithium salts and preparation method thereof |
| CN109742401A (en) * | 2019-01-07 | 2019-05-10 | 中国科学院兰州化学物理研究所 | The compound lithium single ion conductive material of class I organic-inorganic and preparation method |
| JP2019513283A (en) * | 2016-03-18 | 2019-05-23 | ブルー ソリューション | High energy density metal lithium polymer battery |
| CN109921024A (en) * | 2019-03-12 | 2019-06-21 | 北京科技大学 | A kind of flexible solid lithium ion conductor and preparation method thereof applied to battery |
| CN110336080A (en) * | 2019-06-18 | 2019-10-15 | 浙江大学 | A kind of preparation of compound single ion solid electrolyte and application method |
| CN110444808A (en) * | 2019-07-26 | 2019-11-12 | 华中科技大学 | A kind of long-chain branch single-ion polymer electrolyte, its preparation and application |
| CN110783514A (en) * | 2019-02-22 | 2020-02-11 | 张艺莹 | Lithium ion conduction type separator plate, preparation method thereof and battery comprising same |
| CN110964146A (en) * | 2018-09-30 | 2020-04-07 | 上海汽车集团股份有限公司 | Polymer positive electrode material, preparation method thereof and solid-state lithium ion battery |
| CN111019036A (en) * | 2019-12-02 | 2020-04-17 | 常州乾艺智能制造科技有限公司 | Preparation method of nano-grade polymer electrolyte for flexible lithium battery |
| CN111082133A (en) * | 2019-12-02 | 2020-04-28 | 常州乾艺智能制造科技有限公司 | Preparation method of high polymer electrolyte for solid lithium battery |
| CN111106381A (en) * | 2018-10-25 | 2020-05-05 | 深圳市比亚迪锂电池有限公司 | Polymer electrolyte, preparation method thereof and lithium ion battery |
| CN111326788A (en) * | 2020-03-02 | 2020-06-23 | 华中科技大学 | Single-ion polymer electrolyte system and preparation method and application thereof |
| CN111748096A (en) * | 2020-07-08 | 2020-10-09 | 吉林大学 | Preparation and application of polybenzimidazole based single-ion polymer gel electrolyte |
| CN112038690A (en) * | 2019-06-04 | 2020-12-04 | 北京卫蓝新能源科技有限公司 | Boron-containing polymer solid electrolyte and application thereof |
| CN112552438A (en) * | 2019-09-10 | 2021-03-26 | 北京紫藤医创医药信息技术有限公司 | Preparation method of high-molecular polymer electrolyte for flexible lithium battery |
| WO2021129582A1 (en) * | 2019-12-23 | 2021-07-01 | 珠海冠宇电池股份有限公司 | Solid-state polymer electrolyte containing boron-fluorine structure, preparation method therefor, and use thereof |
| CN114300684A (en) * | 2021-12-31 | 2022-04-08 | 珠海冠宇电池股份有限公司 | Single lithium ion polymer lithium-conducting binder and battery containing same |
| CN114335715A (en) * | 2021-12-31 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Single lithium ion polymer electrolyte membrane and battery comprising same |
| CN114335714A (en) * | 2021-12-31 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Single lithium ion polymer electrolyte membrane and battery comprising same |
| US11682793B2 (en) | 2020-10-27 | 2023-06-20 | Ford Global Technologies. Llc | Single-ion polymer electrolyte molecular design |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107317049B (en) * | 2017-05-08 | 2019-07-09 | 浙江大学 | A kind of single ion conductive polymer electrolyte and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640895A (en) * | 2004-12-17 | 2005-07-20 | 华中科技大学 | High-molecular polymer containing perfluoro alkyl sulfimine side-chain and its synthesizing method |
| CN101335365A (en) * | 2007-06-27 | 2008-12-31 | 郑州大学 | Lithium ion polymer electrolyte film and manufacturing method of lithium ion cell comprising the film |
| JP2012107219A (en) * | 2010-10-29 | 2012-06-07 | Asahi Kasei Corp | Ionic polymer |
-
2012
- 2012-07-02 CN CN201210223926.8A patent/CN103509153B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640895A (en) * | 2004-12-17 | 2005-07-20 | 华中科技大学 | High-molecular polymer containing perfluoro alkyl sulfimine side-chain and its synthesizing method |
| CN101335365A (en) * | 2007-06-27 | 2008-12-31 | 郑州大学 | Lithium ion polymer electrolyte film and manufacturing method of lithium ion cell comprising the film |
| JP2012107219A (en) * | 2010-10-29 | 2012-06-07 | Asahi Kasei Corp | Ionic polymer |
Non-Patent Citations (3)
| Title |
|---|
| HARRY R. ALLCOCK ET AL.，: "Single ion conductors—polyphosphazenes with sulfonimide functional groups", 《SOLID STATE IONICS》, vol. 177, no. 78, 15 March 2006 (2006-03-15), pages 741 - 747 * |
| RACHID MEZIANE ET AL.，: "Single-ion polymer electrolytes based on a delocalized polyanion for lithium batteries", 《ELECTROCHIMICA ACTA》, vol. 57, 24 March 2011 (2011-03-24), pages 14 - 19, XP028124235, DOI: 10.1016/j.electacta.2011.03.074 * |
| XIAO-GUANG SUN ET AL.，: "Comb-shaped single ion conductors based on polyacrylate ethers and lithium alkyl sulfonate", 《ELECTROCHIMICA ACTA》, vol. 50, no. 5, 11 September 2004 (2004-09-11), pages 1139 - 1147 * |
Cited By (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9856341B2 (en) | 2014-12-26 | 2018-01-02 | Samsung Electronics Co., Ltd. | Polymer, and electrolyte and lithium secondary battery including the same |
| CN106674391A (en) * | 2015-11-10 | 2017-05-17 | 华中科技大学 | Iamine-polyanion lithium salt and preparation method thereof as well as application of iamine-polyanion lithium salt as nonaqueous electrolyte |
| JP7034930B2 (en) | 2016-03-18 | 2022-03-14 | ブルー ソリューション | High energy density metal lithium polymer battery |
| JP2019513283A (en) * | 2016-03-18 | 2019-05-23 | ブルー ソリューション | High energy density metal lithium polymer battery |
| CN106410270B (en) * | 2016-11-04 | 2018-12-21 | 中山大学 | It is a kind of using carbon dioxide-base polycarbonate as lithium single-ion conductor solid polymer electrolyte of main chain and preparation method thereof |
| KR20180049949A (en) * | 2016-11-04 | 2018-05-14 | 주식회사 엘지화학 | Compound including aromatic ring, polymer including the same |
| KR102141267B1 (en) | 2016-11-04 | 2020-08-04 | 주식회사 엘지화학 | Compound including aromatic ring, polymer including the same |
| CN106410270A (en) * | 2016-11-04 | 2017-02-15 | 中山大学 | Single-lithium-ion-conducting solid polymer electrolyte adopting carbon dioxide based polycarbonate as main chain and preparation method of single-lithium-ion-conducting solid polymer electrolyte |
| CN108155414A (en) * | 2016-12-06 | 2018-06-12 | 中国科学院宁波材料技术与工程研究所 | Fluoropolymer lithium ion conductor, preparation method and the application of self-plasticization |
| CN106711503A (en) * | 2016-12-19 | 2017-05-24 | 西南石油大学 | Single-ion gel polymer electrolyte and preparation method thereof |
| KR20190125420A (en) * | 2017-03-09 | 2019-11-06 | 블루 솔루션즈 캐나다 인크. | Block Copolymer Electrolyte For Lithium Batteries |
| KR102558484B1 (en) | 2017-03-09 | 2023-07-24 | 블루 솔루션즈 캐나다 인크. | Block Copolymer Electrolytes for Lithium Batteries |
| CN110431704B (en) * | 2017-03-09 | 2022-09-20 | 加拿大蓝色解决方案有限公司 | Block copolymer electrolyte for lithium battery |
| WO2018161150A1 (en) * | 2017-03-09 | 2018-09-13 | Blue Solutions Canada Inc. | Block copolymer electrolyte for lithium batteries |
| CN110431704A (en) * | 2017-03-09 | 2019-11-08 | 加拿大蓝色解决方案有限公司 | Block copolymer electrolyte matter for lithium battery |
| US10854919B2 (en) | 2017-03-09 | 2020-12-01 | Blue Solutions Canada Inc. | Block copolymer electrolyte for lithium batteries |
| CN109096433A (en) * | 2017-06-20 | 2018-12-28 | 天津大学 | Single ion conductor polymer lithium salts and preparation method thereof |
| CN108832178A (en) * | 2018-06-20 | 2018-11-16 | 哈尔滨工业大学 | single-ion polymer electrolyte and its preparation method and application |
| CN110964146B (en) * | 2018-09-30 | 2021-07-09 | 上海汽车集团股份有限公司 | Polymer positive electrode material, preparation method thereof and solid-state lithium ion battery |
| CN110964146A (en) * | 2018-09-30 | 2020-04-07 | 上海汽车集团股份有限公司 | Polymer positive electrode material, preparation method thereof and solid-state lithium ion battery |
| CN111106381A (en) * | 2018-10-25 | 2020-05-05 | 深圳市比亚迪锂电池有限公司 | Polymer electrolyte, preparation method thereof and lithium ion battery |
| CN109742401B (en) * | 2019-01-07 | 2021-06-01 | 中国科学院兰州化学物理研究所 | Organic-inorganic composite lithium single-ion conductive material and preparation method thereof |
| CN109742401A (en) * | 2019-01-07 | 2019-05-10 | 中国科学院兰州化学物理研究所 | The compound lithium single ion conductive material of class I organic-inorganic and preparation method |
| CN110783514A (en) * | 2019-02-22 | 2020-02-11 | 张艺莹 | Lithium ion conduction type separator plate, preparation method thereof and battery comprising same |
| CN109921024A (en) * | 2019-03-12 | 2019-06-21 | 北京科技大学 | A kind of flexible solid lithium ion conductor and preparation method thereof applied to battery |
| CN112038690A (en) * | 2019-06-04 | 2020-12-04 | 北京卫蓝新能源科技有限公司 | Boron-containing polymer solid electrolyte and application thereof |
| CN112038690B (en) * | 2019-06-04 | 2022-12-06 | 北京卫蓝新能源科技有限公司 | Boron-containing polymer solid electrolyte and application thereof |
| CN110336080B (en) * | 2019-06-18 | 2020-11-03 | 浙江大学 | Preparation and application method of composite single-ion solid electrolyte |
| CN110336080A (en) * | 2019-06-18 | 2019-10-15 | 浙江大学 | A kind of preparation of compound single ion solid electrolyte and application method |
| CN110444808A (en) * | 2019-07-26 | 2019-11-12 | 华中科技大学 | A kind of long-chain branch single-ion polymer electrolyte, its preparation and application |
| CN112552438A (en) * | 2019-09-10 | 2021-03-26 | 北京紫藤医创医药信息技术有限公司 | Preparation method of high-molecular polymer electrolyte for flexible lithium battery |
| CN112552438B (en) * | 2019-09-10 | 2022-05-27 | 北京紫藤医创医药信息技术有限公司 | Preparation method of high-molecular polymer electrolyte for flexible lithium battery |
| CN111019036B (en) * | 2019-12-02 | 2022-04-19 | 常州乾艺智能制造科技有限公司 | Preparation method of nano-grade polymer electrolyte for flexible lithium battery |
| CN111082133A (en) * | 2019-12-02 | 2020-04-28 | 常州乾艺智能制造科技有限公司 | Preparation method of high polymer electrolyte for solid lithium battery |
| CN111019036A (en) * | 2019-12-02 | 2020-04-17 | 常州乾艺智能制造科技有限公司 | Preparation method of nano-grade polymer electrolyte for flexible lithium battery |
| CN111082133B (en) * | 2019-12-02 | 2022-10-28 | 常州乾艺智能制造科技有限公司 | Preparation method of high polymer electrolyte for solid lithium battery |
| WO2021129582A1 (en) * | 2019-12-23 | 2021-07-01 | 珠海冠宇电池股份有限公司 | Solid-state polymer electrolyte containing boron-fluorine structure, preparation method therefor, and use thereof |
| CN111326788B (en) * | 2020-03-02 | 2021-05-07 | 华中科技大学 | Single-ion polymer electrolyte system and preparation method and application thereof |
| CN111326788A (en) * | 2020-03-02 | 2020-06-23 | 华中科技大学 | Single-ion polymer electrolyte system and preparation method and application thereof |
| CN111748096A (en) * | 2020-07-08 | 2020-10-09 | 吉林大学 | Preparation and application of polybenzimidazole based single-ion polymer gel electrolyte |
| US11682793B2 (en) | 2020-10-27 | 2023-06-20 | Ford Global Technologies. Llc | Single-ion polymer electrolyte molecular design |
| CN114335714A (en) * | 2021-12-31 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Single lithium ion polymer electrolyte membrane and battery comprising same |
| CN114335715A (en) * | 2021-12-31 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Single lithium ion polymer electrolyte membrane and battery comprising same |
| CN114300684A (en) * | 2021-12-31 | 2022-04-08 | 珠海冠宇电池股份有限公司 | Single lithium ion polymer lithium-conducting binder and battery containing same |
| WO2023125545A1 (en) * | 2021-12-31 | 2023-07-06 | 珠海冠宇电池股份有限公司 | Electrolyte membrane and preparation method therefor, and battery |
| CN114335714B (en) * | 2021-12-31 | 2024-04-16 | 珠海冠宇电池股份有限公司 | Single lithium ion polymer electrolyte membrane and battery comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103509153B (en) | 2016-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103509153B (en) | A kind of polymer list ionic electrolytes and preparation method thereof | |
| Niu et al. | In situ copolymerizated gel polymer electrolyte with cross-linked network for sodium-ion batteries | |
| Zhao et al. | Gel polymer electrolyte based on polymethyl methacrylate matrix composited with methacrylisobutyl-polyhedral oligomeric silsesquioxane by phase inversion method | |
| CN109802174A (en) | A kind of preparation and its application of polycarbonate base polymer electrolyte | |
| CN109103488B (en) | Polymer sodium battery and preparation method and application thereof | |
| Stepniak et al. | Characterization and application of N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide ionic liquid–based gel polymer electrolyte prepared in situ by photopolymerization method in lithium ion batteries | |
| CN104031193A (en) | Polymer ion liquid electrolyte and preparation method thereof | |
| KR20160079574A (en) | Polymer, electrolyte comprising the polymer, and lithium secondary battery comprising the electrolyte | |
| CN103570873B (en) | A kind of composition for gel polymer electrolyte, gel polymer electrolyte and electrochemical appliance | |
| RU2388088C1 (en) | New polymer electrolyte and electrochemical device | |
| CN107785609A (en) | The preparation method of full solid state polymer electrolyte and the serondary lithium battery containing the electrolyte | |
| KR20140046611A (en) | Composition for ionic liquid polymer electrolyte, ionic liquid polymer electrolyte prepared therefrom, and lithium secondary cell comprising the same | |
| CN108242563B (en) | High-voltage-resistant solid lithium battery polymer electrolyte and preparation and application thereof | |
| CN106887622B (en) | Fluorine-containing single-ion conductor polymer electrolyte and preparation method and application thereof | |
| CN108923064B (en) | Solid polymer electrolyte, preparation method thereof and lithium ion secondary battery | |
| CN109830743A (en) | Gel polymer electrolyte, lithium ion secondary battery and preparation method | |
| CN104183869A (en) | Lithium single ionic conductive microporous electrolyte membrane and preparation method thereof | |
| CN111786018B (en) | High-voltage polymer electrolyte, high-voltage polymer lithium metal battery and preparation method of battery | |
| CN101381429B (en) | Self-supporting lithium ionic cell gel polymer electrolyte, special polymer and preparation method and application thereof | |
| Yu et al. | Single-ion polyelectrolyte/mesoporous hollow-silica spheres, composite electrolyte membranes for lithium-ion batteries | |
| CN109456484B (en) | Novel fluorine-containing sulfimide single-ion conductor polymer with conjugated structure and preparation method and application thereof | |
| Jing et al. | Highly conductive and mechanically robust single-ion conducting polymer electrolyte membranes with a high concentration of charge carriers for dendrite-proof lithium metal batteries | |
| CN105024094A (en) | Polymer electrolyte containing lithium imide fluorosulfonate and preparing method of polymer electrolyte | |
| CN111613832B (en) | Pentad monomer copolymer lithium secondary battery and preparation method thereof | |
| CN110323491B (en) | Polymer electrolyte, polymer electrolyte membrane, and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220926 Address after: Room 01-01, 8th Floor, Unit C, Building CRO, CRO Office Area, No. 666 Gaoxin Avenue, Donghu New Technology Development Zone, Wuhan City, Hubei Province 430200 Patentee after: Wuhan Ruihua New Energy Technology Co.,Ltd. Address before: 430074 Hubei Province, Wuhan city Hongshan District Luoyu Road No. 1037 Patentee before: HUAZHONG University OF SCIENCE AND TECHNOLOGY |
|
| TR01 | Transfer of patent right |